JP2023532438A - Solid state lithium battery cell, battery comprising said battery cell, and manufacturing process for manufacturing said battery - Google Patents

Solid state lithium battery cell, battery comprising said battery cell, and manufacturing process for manufacturing said battery Download PDF

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JP2023532438A
JP2023532438A JP2022579026A JP2022579026A JP2023532438A JP 2023532438 A JP2023532438 A JP 2023532438A JP 2022579026 A JP2022579026 A JP 2022579026A JP 2022579026 A JP2022579026 A JP 2022579026A JP 2023532438 A JP2023532438 A JP 2023532438A
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electrolyte
lithium
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モハメド チャキール，
アキール ディリープ，
バラジ カルヤナランガン，
マドゥミーター ムラリ－エー，
ジャヤント－ラマスワミ ラママーシー，
コンダ－シヴァ レッディ，
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Renault SAS
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Abstract

エッチングされた銅基板（１５）、グラファイト層（１４）、電解質（１２）、ならびにニッケル、マンガン、およびコバルトの酸化物の層（１１）を積層することによって形成され、電解質（１２）が、グラファイト層（１４）ならびにニッケル、マンガン、およびコバルトの酸化物の層（１１）と接触しており、銅基板（１５）が電池セルのアノードを形成し、ニッケル、マンガン、およびコバルトの酸化物の層（１１）が電池セルのカソードを形成する、固体リチウム電池セルであって、電解質（１２）が固体リチウム系電解質であり、グラファイト層（１５）が、液体リチウム系電解質を用いたプレリチウム化中に生成される第１の固体電解質界面（１６）と、固体リチウム系電解質を用いたプレリチウム化中に生成される第２の固体電解質界面（１７）とを有する、固体リチウム電池セルが開示される。【選択図】図２formed by stacking an etched copper substrate (15), a graphite layer (14), an electrolyte (12), and a layer (11) of oxides of nickel, manganese and cobalt, the electrolyte (12) being graphite In contact with the layer (14) and the layer (11) of oxides of nickel, manganese and cobalt, the copper substrate (15) forms the anode of the battery cell and the layer of oxides of nickel, manganese and cobalt. A solid lithium battery cell, wherein (11) forms the cathode of the battery cell, the electrolyte (12) is a solid lithium-based electrolyte, and the graphite layer (15) is during prelithiation with a liquid lithium-based electrolyte. A solid state lithium battery cell is disclosed having a first solid electrolyte interface (16) produced during prelithiation with a solid lithium based electrolyte and a second solid electrolyte interface (17) produced during prelithiation with a solid lithium based electrolyte. be. [Selection drawing] Fig. 2

Description

本発明は、リチウム電池に関し、特に固体リチウム電池に関する。 The present invention relates to lithium batteries, and more particularly to solid state lithium batteries.

固体電解質電池技術により、既存の電池の容量およびその動作の安全性を、特にリチウムイオン電池の場合に、液体電解質電池と比較して改善することが可能になると予期されている。 Solid electrolyte battery technology is expected to allow improvements in the capacity of existing batteries and their operational safety, especially in the case of lithium-ion batteries, compared to liquid electrolyte batteries.

従来の固体リチウム電池は、液体電解質リチウムイオン電池の場合と同様に、カソードと、固体ポリマー電解質と、アノードとを備える。より具体的には、固体リチウム電池は、アノード、電解質、およびカソードを、アノードを銅基板と接触させカソードをアルミニウム基板と接触させて、銅基板とアルミニウム基板との間に積層することによって製造される。 A conventional solid state lithium battery comprises a cathode, a solid polymer electrolyte, and an anode, as in liquid electrolyte lithium ion batteries. More specifically, solid state lithium batteries are manufactured by laminating an anode, an electrolyte, and a cathode between a copper substrate and an aluminum substrate, with the anode in contact with the copper substrate and the cathode in contact with the aluminum substrate. be.

アノードはグラファイトで構成することができ、固体ポリマー電解質は、ＰＶＤＦ－ＨＦＰ（ポリ（フッ化ビニリデン）－コ－ポリ（ヘキサフルオロプロピレン））、ＬＩＴＦＳＩ（リチウムビス（トリフルオロメチルスルホニル）イミド）、およびＴＥＧ－ＤＭＥ（テトラエチレングリコールジメチルエーテル）を含む化合物である。 The anode can be composed of graphite and the solid polymer electrolytes are PVDF-HFP (poly(vinylidene fluoride)-co-poly(hexafluoropropylene)), LITFSI (lithium bis(trifluoromethylsulfonyl)imide), and It is a compound containing TEG-DME (tetraethylene glycol dimethyl ether).

固体リチウム電池によって予期することができる改善にかかわらず、使用可能な電池を得る前にグラファイト電解質界面を改善することがまだ必要である。電池は、現在の状態では、利用可能である量以上にリチウムイオンを消費するグラファイト電解質界面を備え、それがリチウムイオンの移動を妨げている。この結果、ＳＥＩ（固体電解質界面）が形成され、充電または放電を実施することが不可能になる。 Despite the improvements that can be expected with solid state lithium batteries, there is still a need to improve the graphite electrolyte interface before obtaining usable batteries. Batteries, in their current state, have a graphite electrolyte interface that consumes more lithium ions than is available, which impedes the migration of lithium ions. As a result, an SEI (Solid Electrolyte Interface) is formed, making it impossible to carry out charging or discharging.

加えて、剥離によって、銅基板とグラファイトアノードとの間の界面に第２の問題が存在する。グラファイト電極のプレリチウム化中に、グラファイト電極と銅基板との間の界面には溶剤がリチウムイオンと同時挿入される。この結果、プレリチウム化電極のフレーキングおよびフラグメンテーションが起こり、電極が損傷し不適切なものになる。 In addition, delamination presents a second problem at the interface between the copper substrate and the graphite anode. During prelithiation of the graphite electrode, a solvent is co-intercalated with lithium ions at the interface between the graphite electrode and the copper substrate. This results in flaking and fragmentation of the prelithiated electrode, making the electrode damaged and unsuitable.

換言すれば、リチウムイオンがグラファイトアノードと銅基板との間に挿入されて、銅基板に対するグラファイトアノードの接着が低減され、それがフレーキングにつながる。 In other words, lithium ions are intercalated between the graphite anode and the copper substrate to reduce the adhesion of the graphite anode to the copper substrate, which leads to flaking.

グラファイトアノードを構造的に損傷することに加えて、この挿入（またはインターカレーション）の作用によって、グラファイトアノードの接触抵抗がより大きくなり、充電および放電容量がさらに低減される。 In addition to structurally damaging the graphite anode, this intercalation effect results in higher graphite anode contact resistance, further reducing charge and discharge capacity.

結果として、理論的に予測される容量と比較して容量が少ないかまたは容量がない、固体リチウム電池に関する問題が存在する。 As a result, there is a problem with solid state lithium batteries that have little or no capacity compared to what is theoretically predicted.

ＳＥＩを形成するための第１のサイクル中に消費されるリチウムの量を低減するために、固体電解質電池の製造に対して、グラファイトアノードのプレリチウム化の段階が提案されてきた。電気化学プロセスを用いた、最終セルの外部におけるグラファイトアノードのプレリチウム化は、特許および科学文献によって知られている。 In order to reduce the amount of lithium consumed during the first cycle to form the SEI, a stage of prelithiation of graphite anodes has been proposed for the manufacture of solid electrolyte cells. Prelithiation of graphite anodes outside the final cell using electrochemical processes is known from the patent and scientific literature.

特に、文献ＵＳ ５ ７５９ ７１５ Ａは、最新技術によって知られており、このプレリチウム化段階を第１の電池セルで実施し、プレリチウム化されたアノードを取り除き、次に最終セルをプレリチウム化アノードとともに組み立てるためのプロセスを記載している。 In particular, the document US 5 759 715 A is known from the state of the art, performing this prelithiation step on the first battery cell, removing the prelithiated anode and then prelithiating the final cell. A process for assembly with an anode is described.

文献ＵＳ ５ ７５９ ７１５ Ａは、最終セルまたは電池を組み立てる前に、「前駆」セルでプレリチウム化された少なくとも１つの電極を有する、電気化学セルを構築するためのプロセスを開示している。好ましくは、活物質Ｖ６Ｏ１３もしくはグラファイト、または両方の粒子は、最終セルを組み立てる前に、プレリチウム化によって「前駆」セル内で作製される。かかるプレリチウム化は、リチウムイオンをグラファイト電極に化学的または電気化学的に挿入することによって得られる。 Document US 5 759 715 A discloses a process for constructing an electrochemical cell having at least one electrode prelithiated in a "precursor" cell prior to assembly of the final cell or battery. Preferably, the particles of active material V 6 O 13 or graphite, or both, are made in the “precursor” cell by prelithiation before assembling the final cell. Such prelithiation is obtained by chemically or electrochemically inserting lithium ions into graphite electrodes.

しかしながら、これらの文献はいずれも、上記に特定した技術的課題に対処していない。 However, none of these documents address the technical problems identified above.

本発明の主題は、エッチングされた銅基板、グラファイト層、電解質、ならびにニッケル、マンガン、およびコバルトの酸化物の層を積層することによって形成され、電解質が、グラファイト層ならびにニッケル、マンガン、およびコバルトの酸化物の層と接触しており、銅基板が電池セルのアノードを形成し、ニッケル、マンガン、およびコバルトの酸化物の層が電池セルのカソードを形成する、固体リチウム電池セルである。電解質は固体リチウム系電解質であり、グラファイト層は、液体リチウム系電解質を用いたプレリチウム化中に生成される第１の固体電解質界面と、固体リチウム系電解質を用いたプレリチウム化中に生成される第２の固体電解質界面とを呈する。 The subject matter of the present invention is formed by laminating an etched copper substrate, a graphite layer, an electrolyte, and layers of oxides of nickel, manganese, and cobalt, wherein the electrolyte comprises a graphite layer and nickel, manganese, and cobalt oxides. A solid state lithium battery cell in contact with a layer of oxide, with a copper substrate forming the anode of the battery cell and a layer of oxides of nickel, manganese and cobalt forming the cathode of the battery cell. The electrolyte is a solid lithium-based electrolyte, and the graphite layer is formed at a first solid electrolyte interface formed during prelithiation with a liquid lithium-based electrolyte and during prelithiation with a solid lithium-based electrolyte. and a second solid electrolyte interface.

固体リチウム電解質は、リチウムビス（トリフルオロメチルスルホニル）イミドで改良したポリ（フッ化ビニリデン）－ポリ（ヘキサフルオロプロピレン）で作られた多孔質膜電解質であることができる。 The solid lithium electrolyte can be a porous membrane electrolyte made of poly(vinylidene fluoride)-poly(hexafluoropropylene) modified with lithium bis(trifluoromethylsulfonyl)imide.

銅基板およびグラファイト層は機械的に統合することができる。 The copper substrate and graphite layer can be mechanically integrated.

ニッケル、マンガン、およびコバルトの酸化物の層は、化学式ＬｉＮｉｘＭｎｙＣｏｚＯ２を有することができ、式中、ｘ、ｙ、およびｚは原子パーセント値を表し、ｘは０．３から０．８の間、ｙは０．１から０．３の間、ｚは０．１から０．３の間である。 The layer of oxides of nickel, manganese, and cobalt can have the chemical formula LiNixMnyCozO2 , where x , y , and z represent atomic percent values , and x ranges from 0.3 to is between 0.8, y is between 0.1 and 0.3, and z is between 0.1 and 0.3.

固体リチウム電池は、並列に嵌め込まれた、上述したものなどの電池セルを少なくとも２つ備えることができる。 A solid state lithium battery can comprise at least two battery cells, such as those described above, fitted in parallel.

本発明の別の主題は、
レリーフパターンを得るために、銅基板のウェットエッチングを実施する段階と、
エッチングされた銅基板上にグラファイト層を配置する段階と、
エッチングされた銅基板上のグラファイト層と、ニッケル、マンガン、およびコバルトの酸化物の層と、グラファイト層ならびにニッケル、マンガン、およびコバルトの酸化物の層の両方と接触している液体リチウム系電解質とを備える第１の電池セルを組み立てる段階と、
第１の電池セルのグラファイト層のプレリチウム化を実施する段階と、
第１の電池セルから、エッチングされた銅基板に固定されたプレリチウム化グラファイト層を取り除く段階と、
エッチングされた銅基板上のプレリチウム化グラファイト層と、ニッケル、マンガン、およびコバルトの酸化物の層と、プレリチウム化グラファイト層ならびにニッケル、マンガン、およびコバルトの酸化物の層と接触している固体リチウム系電解質とを備える第２の電池セルを組み立てる段階と、
少なくとも２つの第２の電池セルを並列で備える固体リチウム電池を組み立てる段階と、を含む、上述したような固体リチウム電池を製造する製造プロセスである。 Another subject of the invention is
performing a wet etching of the copper substrate to obtain a relief pattern;
placing a graphite layer on an etched copper substrate;
A layer of graphite on an etched copper substrate, a layer of nickel, manganese and cobalt oxides, and a liquid lithium-based electrolyte in contact with both the graphite layer and the layer of nickel, manganese and cobalt oxides. assembling a first battery cell comprising
performing prelithiation of the graphite layer of the first battery cell;
removing the prelithiated graphite layer fixed to the etched copper substrate from the first battery cell;
A layer of prelithiated graphite and a layer of oxides of nickel, manganese and cobalt on an etched copper substrate and a solid in contact with the layer of prelithiated graphite and a layer of oxides of nickel, manganese and cobalt assembling a second battery cell comprising a lithium-based electrolyte;
assembling a solid state lithium battery comprising at least two second battery cells in parallel.

第１の電池セルのプレリチウム化は、放電サイクルを用いて、周囲温度および電圧ウィンドウＯＣＶ －１０ｍＶで０．０５Ｃの定電流定電圧モードで実施することができる。 Prelithiation of the first battery cell can be performed in constant current constant voltage mode at 0.05 C at ambient temperature and voltage window OCV -10 mV using discharge cycles.

銅基板のエッチングは、
ＦｅＣｌ３、ＨＣｌ、およびＨ２Ｏの溶液を３０秒間適用する段階と、
銅基板を炭酸水素アンモニウムＮＨ４ＨＣＯ３溶液で、次に水で洗浄する段階と、
銅基板を熱板の上で８０℃で乾燥させる段階と、を含むことができる。 Etching the copper substrate
applying a solution of FeCl 3 , HCl, and H 2 O for 30 seconds;
washing the copper substrate with an ammonium bicarbonate NH 4 HCO 3 solution and then with water;
drying the copper substrate on a hot plate at 80°C.

固体リチウム系電解質は乾燥ポリマー電解質であることができる。 The solid lithium-based electrolyte can be a dry polymer electrolyte.

固体リチウム系電解質は、リチウムビス（トリフルオロメチルスルホニル）イミドで改良したポリ（フッ化ビニリデン）－ポリ（ヘキサフルオロプロピレン）で作られた多孔質膜電解質であることができる。 The solid lithium-based electrolyte can be a porous membrane electrolyte made of poly(vinylidene fluoride)-poly(hexafluoropropylene) modified with lithium bis(trifluoromethylsulfonyl)imide.

本発明のより良い理解は、完全な非現定例を用いて考察され添付図面によって例証される多数の実施形態の詳細な説明を検討することで得られるであろう。 A better understanding of the present invention will be obtained from a consideration of the detailed description of a number of embodiments discussed using a complete non-current example and illustrated by the accompanying drawings.

本発明による製造プロセスの主要段階を示す図である。1 shows the main stages of the manufacturing process according to the invention; FIG. 本発明による二層ＳＥＩ電池セルの主要部分を示す図である。FIG. 2 shows the main parts of a dual-layer SEI battery cell according to the invention;

銅基板上のグラファイト層のフレーキングの問題を解決するために、グラファイト層の形成前に、銅基板の化学エッチングが実施される。このエッチングは、特に銅基板の表面のくぼみにより、レリーフパターンを形成するように設計される。グラファイト層のコーティング中に、くぼみがグラファイトで充填されることにより、相互の機械的係止によってグラファイト層の取付けが可能になる。換言すれば、接着力が生じる総表面積が増加する。 In order to solve the problem of flaking of the graphite layer on the copper substrate, chemical etching of the copper substrate is performed before forming the graphite layer. This etch is specifically designed to form a relief pattern by recessing the surface of the copper substrate. Filling of the depressions with graphite during the coating of the graphite layers allows attachment of the graphite layers by mutual mechanical locking. In other words, the total surface area over which adhesion forces occur increases.

エッチングは、ＦｅＣｌ３、ＨＣｌ、およびＨ２Ｏの溶液を用いたウェットエッチングの形態で実施される。エッチング溶液は、３０秒間にわたって銅基板に適用される。続いて、銅基板は、炭酸水素アンモニウムＮＨ４ＨＣＯ３溶液で、次に水で連続して洗浄される。続いて、銅基板は、熱板の上で８０℃で乾燥される。 Etching is performed in the form of a wet etch using a solution of FeCl3 , HCl and H2O . The etching solution is applied to the copper substrate for 30 seconds. Subsequently, the copper substrate is washed successively with an ammonium bicarbonate NH 4 HCO 3 solution and then with water. The copper substrate is then dried on a hot plate at 80°C.

ＳＥＩの問題を解決するために、二層ＳＥＩが設計された。 A two-layer SEI was designed to solve the SEI problem.

第１の段階中に、ニッケル、マンガン、およびコバルト（ＮＭＣ）の酸化物の層と、グラファイト層と、それらの間の液体リチウム系電解質とを備える層の積層体が形成される。ニッケル、マンガン、およびコバルトの酸化物の層は、化学式ＬｉＮｉｘＭｎｙＣｏｚＯ２であり、式中、ｘ、ｙ、およびｚは原子パーセント値を表し、ｘは０．３から０．８の間、ｙは０．１から０．３の間、ｚは０．１から０．３の間である。 During the first stage, a stack of layers is formed comprising a layer of oxides of nickel, manganese and cobalt (NMC), a layer of graphite and a liquid lithium-based electrolyte therebetween. The layer of oxides of nickel, manganese, and cobalt has the chemical formula LiNixMnyCozO2 , where x , y , and z represent atomic percent values, and x is 0.3 to 0.8. , y is between 0.1 and 0.3, and z is between 0.1 and 0.3.

グラファイト電極のプレリチウム化後、第１のＳＥＩが形成される。続いて、電池セルは、液体電解質／グラファイト電極ＳＥＩを取り除くために切断される。 After prelithiation of the graphite electrode, a first SEI is formed. The battery cell is then cut to remove the liquid electrolyte/graphite electrode SEI.

第２の段階中に、第１の電池セルから取り除かれた液体電解質／グラファイト電極ＳＥＩで第２の電池セルが構築される。第２の電池セルは、第１の電池セルと類似しているが、液体リチウム系電解質の代わりにポリマーリチウム系電解質を含む構造を備える。第２の電池セルのグラファイト層をプレリチウム化した後、液体電解質ＳＥＩと固体ポリマー電解質との間の界面に第２のＳＥＩが形成される。 During the second phase, a second battery cell is constructed with the liquid electrolyte/graphite electrode SEI removed from the first battery cell. The second battery cell is similar to the first battery cell, but has a structure that includes a polymeric lithium-based electrolyte instead of a liquid lithium-based electrolyte. After prelithiation of the graphite layer of the second battery cell, a second SEI is formed at the interface between the liquid electrolyte SEI and the solid polymer electrolyte.

得られた二層ＳＥＩにより、安定したグラファイトと電解質との間でのイオンの移動が可能になる。 The resulting bilayer SEI allows ionic transfer between the stable graphite and the electrolyte.

固体リチウム電池を製造するためのプロセスは、以下の段階を含む。 A process for manufacturing a solid state lithium battery includes the following steps.

第１の段階１の間に、銅基板が、ＦｅＣｌ３、ＨＣｌ、およびＨ２Ｏ（ＦｅＣｌ３：０．５～１ｇ、３６％ＨＣｌ：３～５ｍｌ、Ｈ２Ｏ：１２～１５ｍｌ）の溶液でウェットエッチングされる。 During the first stage 1, the copper substrate was immersed in a solution of FeCl 3 , HCl and H 2 O (FeCl 3 : 0.5-1 g, 36% HCl: 3-5 ml, H 2 O: 12-15 ml). is wet etched.

第２の段階２の間に、グラファイト層がエッチングされた銅基板に適用される。 During the second step 2, a graphite layer is applied to the etched copper substrate.

第３の段階３の間に、エッチングされた銅基板上のグラファイト層と、ＮＭＣ層と、グラファイト層およびＮＭＣ層の両方と接触している液体リチウム系電解質とを備える、第１の電池セルが組み立てられる。 During a third stage 3, a first battery cell comprising a graphite layer on an etched copper substrate, an NMC layer, and a liquid lithium-based electrolyte in contact with both the graphite layer and the NMC layer Assembled.

第４の段階４の間に、グラファイト層のプレリチウム化が、周囲温度および電圧ウィンドウＯＣＶ －１０ｍＶで０．０５Ｃの定電流定電圧（ＣＣＣＶ）モードで、放電サイクルを用いて第１の電池セルで実施される。 During the fourth stage 4, the prelithiation of the graphite layer was performed on the first battery cell using a discharge cycle in constant current constant voltage (CCCV) mode at 0.05 C at ambient temperature and voltage window OCV −10 mV. carried out in

第５の段階５の間に、電池セルが開かれ、エッチングされた銅基板上にあるプレリチウム化グラファイト層が取り除かれる。 During the fifth step 5, the battery cell is opened and the prelithiated graphite layer on the etched copper substrate is removed.

第６の段階６の間に、エッチングされた銅基板上のプレリチウム化グラファイト層と、ＮＭＣ層と、プレリチウム化グラファイト層およびＮＭＣ層と接触している固体リチウム系電解質とを備える、第２の電池セルが組み立てられる。固体リチウム系電解質は、ＰＶＤＦ－ＨＦＰ ＬｉＴＦＳＩの名称でも知られる、リチウムビス（トリフルオロメチルスルホニル）イミド（ＬｉＴＦＳＩ）で改良したポリ（フッ化ビニリデン）－ポリ（ヘキサフルオロプロピレン）（ＰＶＤＨ－ＨＦＰ）で作られた多孔質膜電解質などの、乾燥ポリマー電解質である。第２の固体電解質界面層は第１の充電中に形成される。 During a sixth stage 6, a second of battery cells are assembled. The solid lithium-based electrolyte is poly(vinylidene fluoride)-poly(hexafluoropropylene) (PVDH-HFP) modified with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), also known as PVDF-HFP LiTFSI. Dry polymer electrolytes, such as fabricated porous membrane electrolytes. A second solid electrolyte interfacial layer is formed during the first charge.

第７の段階７の間に、少なくとも２つの電池セルを並列で備える固体リチウム電池が組み立てられる。 During a seventh stage 7 a solid state lithium battery comprising at least two battery cells in parallel is assembled.

図２は、製造プロセスを用いて得られる第２の電池セルを表している。第２の電池セル１０は、ＮＭＣ層１１と、固体リチウム系電解質１２と、二層ＳＥＩ １３と、グラファイト層１４と、銅基板１５とを備える。二層ＳＥＩ １３は、グラファイト層１４と接触している液体電解質ＳＥＩ １７と、固体リチウム系電解質１２と接触している固体電解質ＳＥＩ １６とを備える。ＮＭＣ層１１は第２の電池セルのカソードを形成し、プレリチウム化グラファイトはアノードを形成する。
FIG. 2 represents a second battery cell obtained using the manufacturing process. A second battery cell 10 comprises an NMC layer 11 , a solid lithium-based electrolyte 12 , a bilayer SEI 13 , a graphite layer 14 and a copper substrate 15 . The bilayer SEI 13 comprises a liquid electrolyte SEI 17 in contact with the graphite layer 14 and a solid electrolyte SEI 16 in contact with the solid lithium-based electrolyte 12 . The NMC layer 11 forms the cathode of the second battery cell and the prelithiated graphite forms the anode.

Claims (10)

エッチングされた銅基板（１５）、グラファイト層（１４）、電解質（１２）、ならびにニッケル、マンガン、およびコバルトの酸化物の層（１１）を積層することによって形成され、前記電解質（１２）が、前記グラファイト層（１４）ならびに前記ニッケル、マンガン、およびコバルトの酸化物の層（１１）と接触しており、前記銅基板（１５）が電池セルのアノードを形成し、前記ニッケル、マンガン、およびコバルトの酸化物の層（１１）が電池セルのカソードを形成する、固体リチウム電池セルであって、前記電解質（１２）が固体リチウム系電解質であり、前記グラファイト層（１４）が、液体リチウム系電解質を用いたプレリチウム化中に生成される第１の固体電解質界面（１６）と、前記固体リチウム系電解質を用いたプレリチウム化中に生成される第２の固体電解質界面（１７）とを呈する、固体リチウム電池セル。 formed by stacking an etched copper substrate (15), a graphite layer (14), an electrolyte (12) and a layer (11) of oxides of nickel, manganese and cobalt, said electrolyte (12) comprising: in contact with said graphite layer (14) and said oxide layer (11) of nickel, manganese and cobalt, said copper substrate (15) forming the anode of a battery cell, said nickel, manganese and cobalt A solid lithium battery cell, wherein a layer (11) of oxide of (11) forms the cathode of the battery cell, said electrolyte (12) is a solid lithium-based electrolyte and said graphite layer (14) is a liquid lithium-based electrolyte and a second solid electrolyte interface (17) produced during prelithiation with said solid lithium-based electrolyte. , solid-state lithium battery cells. 前記固体リチウム系電解質（１２）が、リチウムビス（トリフルオロメチルスルホニル）イミドで改良したポリ（フッ化ビニリデン）－ポリ（ヘキサフルオロプロピレン）で作られた多孔質膜電解質である、請求項１に記載の固体リチウム電池セル。 2. The method of claim 1, wherein the solid lithium-based electrolyte (12) is a porous membrane electrolyte made of poly(vinylidene fluoride)-poly(hexafluoropropylene) modified with lithium bis(trifluoromethylsulfonyl)imide. Solid state lithium battery cell as described. 前記銅基板および前記グラファイト層が機械的に統合される、請求項１または２に記載の固体リチウム電池セル。 3. The solid state lithium battery cell of claim 1 or 2, wherein said copper substrate and said graphite layer are mechanically integrated. 前記ニッケル、マンガン、およびコバルトの酸化物の層（１１）が、化学式ＬｉＮｉｘＭｎｙＣｏｚＯ２のものであり、式中、ｘ、ｙ、およびｚが原子パーセント値を表し、ｘが０．３から０．８の間、ｙが０．１から０．３の間、ｚが０．１から０．３の間である、請求項１から３のいずれか一項に記載の固体リチウム電池セル。 Said nickel, manganese and cobalt oxide layer (11) is of the chemical formula LiNixMnyCozO2 , where x, y and z represent atomic percentage values and x is 0 Solid state lithium according to any one of claims 1 to 3, wherein y is between 0.1 and 0.3 and z is between 0.1 and 0.3. battery cell. 請求項１から４のいずれか一項に記載の電池セルを少なくとも２つ備え、前記電池セルが並列に嵌め込まれた、固体リチウム電池。 A solid state lithium battery comprising at least two battery cells according to any one of claims 1 to 4, said battery cells being fitted in parallel. 請求項５に記載の固体リチウム電池を製造する製造プロセスであって、
レリーフパターンを得るために、銅基板のウェットエッチングを実施する段階と、
エッチングされた前記銅基板上にグラファイト層を配置する段階と、
前記エッチングされた銅基板上の前記グラファイト層と、ニッケル、マンガン、およびコバルトの酸化物の層と、前記グラファイト層ならびに前記ニッケル、マンガン、およびコバルトの酸化物の層の両方と接触している液体リチウム系電解質とを備える第１の電池セルを組み立てる段階と、
前記第１の電池セルの前記グラファイト層のプレリチウム化を実施する段階と、
前記第１の電池セルから、前記エッチングされた銅基板に固定された、プレリチウム化された前記グラファイト層を取り除く段階と、
前記エッチングされた銅基板上の前記プレリチウム化されたグラファイト層と、ニッケル、マンガン、およびコバルトの酸化物の層と、前記プレリチウム化されたグラファイト層ならびに前記ニッケル、マンガン、およびコバルトの酸化物の層と接触している固体リチウム系電解質とを備える第２の電池セルを組み立てる段階と、
少なくとも２つの第２の電池セルを並列で備える固体リチウム電池を組み立てる段階と、
を含む、製造プロセス。 A manufacturing process for manufacturing the solid state lithium battery of claim 5, comprising:
performing a wet etching of the copper substrate to obtain a relief pattern;
placing a graphite layer on the etched copper substrate;
a liquid in contact with both the graphite layer, the nickel, manganese and cobalt oxide layer and the nickel, manganese and cobalt oxide layer on the etched copper substrate; assembling a first battery cell comprising a lithium-based electrolyte;
performing prelithiation of the graphite layer of the first battery cell;
removing the prelithiated graphite layer fixed to the etched copper substrate from the first battery cell;
said prelithiated graphite layer on said etched copper substrate; a layer of oxides of nickel, manganese and cobalt; said prelithiated graphite layer and said oxides of nickel, manganese and cobalt; assembling a second battery cell comprising a solid lithium-based electrolyte in contact with a layer of
assembling a solid state lithium battery comprising at least two second battery cells in parallel;
manufacturing process, including; 前記第１の電池セルの前記プレリチウム化が、周囲温度および電圧ウィンドウＯＣＶ －１０ｍＶで０．０５Ｃの定電流定電圧モードで、放電サイクルを用いて実施される、請求項６に記載の固体リチウム電池を製造する製造プロセス。 7. Solid state lithium according to claim 6, wherein said prelithiation of said first battery cell is carried out using a discharge cycle in constant current constant voltage mode at 0.05 C at ambient temperature and voltage window OCV -10 mV. The manufacturing process that makes batteries. 前記銅基板の前記エッチングが、
ＦｅＣｌ３、ＨＣｌ、およびＨ２Ｏの溶液を３０秒間適用する段階と、
前記銅基板を炭酸水素アンモニウムＮＨ４ＨＣＯ３溶液で、次に水で洗浄する段階と、
前記銅基板を熱板の上で８０℃で乾燥させる段階と、
を含む、請求項６または７に記載の固体リチウム電池を製造する製造プロセス。 The etching of the copper substrate comprises:
applying a solution of FeCl 3 , HCl, and H 2 O for 30 seconds;
washing the copper substrate with an ammonium bicarbonate NH 4 HCO 3 solution and then with water;
drying the copper substrate on a hot plate at 80° C.;
A manufacturing process for manufacturing a solid state lithium battery according to claim 6 or 7, comprising: 前記固体リチウム系電解質が乾燥ポリマー電解質である、請求項６から８のいずれか一項に記載の固体リチウム電池を製造する製造プロセス。 A manufacturing process for manufacturing a solid state lithium battery according to any one of claims 6 to 8, wherein the solid state lithium based electrolyte is a dry polymer electrolyte. 前記固体リチウム系電解質が、リチウムビス（トリフルオロメチルスルホニル）イミドで改良したポリ（フッ化ビニリデン）－ポリ（ヘキサフルオロプロピレン）で作られた多孔質膜電解質である、請求項９に記載の固体リチウム電池を製造する製造プロセス。
The solid state of claim 9, wherein the solid state lithium-based electrolyte is a porous membrane electrolyte made of poly(vinylidene fluoride)-poly(hexafluoropropylene) modified with lithium bis(trifluoromethylsulfonyl)imide. The manufacturing process that produces lithium batteries.
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